Methods of reducing color in alkanolamine compositions and compositions produced thereby

ABSTRACT

A method of reducing color in an alkanolamine, the method comprising: contacting the alkanolamine with an amount of an aqueous solution effective to provide 5 to 1000 parts per million by weight of an alkali metal borohydride, based on parts by weight of the alkanolamine; and 0.5 to 10,000 parts per million by weight of an alkali metal hydroxide, based on parts by weight of the alkanolamine; preferably wherein the color-reduced alkanolamine is not distilled after the contacting.

BACKGROUND

This disclosure relates to methods of reducing color in alkanolaminecompositions and the color-reduced compositions produced thereby.

Alkanolamines such as triethanolamine are used primarily as emulsifiersand surfactants in a wide variety of industrial and consumer productapplications. Such applications include household goods, for exampledishwashing liquids, detergents, cleaners, polishes, cement production,cosmetics such as personal care products including shaving creams,medicine, printing, metalworking fluids, paints, lubricants, andelectroless plating, to name a few. A key property to assess the quality(and thus value) of pure alkanolamines such as triethanolamine is color.In general, the less color, the higher its value. Thus, alkanolamineproducers commonly have two objectives in providing pure alkanolamines:inhibiting color formation, and reducing color in discoloredalkanolamines. Both of these objectives are referred to herein as“reducing color.”

Fractional distillation of crude alkanolamines such as triethanolaminecan readily produce a pure product that is initially colorless or nearcolorless. Such initially colorless product, however, can graduallydevelop color during storage, even upon storage in sealed containers inthe dark. This color development can include initial pinking, followedby yellowing, cumulative yellowing, and further darkening to the extentof eventual formation of a brown color. Discoloration is even more rapidif the alkanolamine is exposed to light. The phenomenon of alkanolaminessuch as triethanolamine and other ethanolamines turning color isdescribed, for example, in “SRI International, Process Economics ProgramReport No. 193” of January 1991, pp. 6-9 and 6-10.

Various methods to reduce color in triethanolamine have generally notbeen entirely satisfactory for various reasons. A number of methodssuffer from the drawback that they do not sufficiently remove color fromdiscolored triethanolamine to the extent desired to give a colorless ornear colorless product. Other methods can reduce color but cannotmaintain a color-free product after color removal for a desired periodof time. Moreover, certain methods to reduce color in triethanolaminehave recently raised environmental and health concerns.

Some techniques for reducing color in alkanolamines such astriethanolamine require two-stage vacuum distillation as described inU.S. Pat. No. 7,164,044; use of a rectifying device as described inCN201524433U; use of a two-serial mixing and displacement apparatus asdescribed in RU2430085C1; using a device for continuous manufacture andseparation of triethanolamine as described in U.S. 2004/0127748A1; useof equipment made from substantially nickel-free alloy steel asdescribed in U.S. Pat. No. 4,567,303; use of dividing wall columns asdescribed in U.S. 2014/0061020A1 and CA2540246A1; use of a devicecomprising a distillation column and a downstream column as described inU.S. Pat. No. 8,466,323; as well as use of electromagnetic radiation,third column distillation, and short path and thin film evaporators.Disadvantages associated with these techniques include high investmentcost for special equipment, cost for disposal of spent reagent after itsuse, as well as handling of hazardous materials.

There accordingly remains a need in the art for methods of reducingcolor in alkanolamines such as triethanolamine, for maintaining reducedcolor in alkanolamines, as well as such color-reduced compositions.

SUMMARY

In an embodiment, a method of reducing color in an alkanolaminecomprises contacting the alkanolamine with an amount of an aqueoussolution effective to provide 5 to 1000 parts per million by weight ofan alkali metal borohydride, based on parts by weight of thealkanolamine; and 0.5 to 10,000 parts per million by weight of an alkalimetal hydroxide, based on parts by weight of the alkanolamine,preferably wherein the contacted alkanolamine is not further distilled.

Also disclosed herein is a color-reduced alkanolamine compositioncomprising in combination: an alkanolamine, and an aqueous solution inan amount effective to provide 5 to 1000 parts per million by weight ofan alkali metal borohydride, based on parts by weight of thealkanolamine; and 0.5 to 10,000 parts per million by weight of an alkalimetal hydroxide, based on parts by weight of the alkanolamine,preferably wherein the color-reduced alkanolamine composition has notbeen distilled after manufacture of the alkanolamine.

The above described and other features are exemplified by the followingdetailed description.

DETAILED DESCRIPTION

As described above, unacceptable levels of color and color bodies can befound even in finished, purified alkanolamines. Additionally, colorbodies can form as contaminants over a period of time, for exampleduring storage. The inventors hereof have discovered methods of reducingcolor in alkanolamines, or maintaining reduced color in alkanolamines.The alkanolamine is contacted with an aqueous solution of an alkalimetal borohydride and an alkali metal hydroxide, to providecolor-reduced alkanolamine compositions. For example, the color value ofthe triethanolamine can be reduced from an initial Pt—Co color value of23 to a Pt—Co color value of 5 using these methods. In an advantageousand surprising feature, the alkanolamine as manufactured can becontacted, not subsequently distilled, and still maintain excellentcolor.

Advantageously, after contacting, these alkanolamine compositions arecolorless or near colorless to the human eye. The compositions have aPlatinum-Cobalt Color Value of less than 50, or less than 30, or 0 to20, as determined according to Test Method ASTM D1209. In an especiallyadvantageous feature, the low color can be maintained over months oryears. Thus, in compositions treated to reduce color, or already havingreduced color, the method can be used to maintain the low color overtime. In another advantageous feature, the method is fast, and does notrequire expensive or time-consuming equipment. The color-reducedcompositions can be stored, directly packaged, or transported, forexample.

Further advantageously, an aqueous solution of alkali metal borohydrideand alkali metal hydroxide can effectively reduce the color oftriethanolamine, as determined according to Test Method ASTM D1209, in avery short amount of time. For example, six hours after an aqueoussolution of an alkali metal borohydride and an alkali metal hydroxide isadded to triethanolamine, the color value of the triethanolamine can be50%, 30%, 25%, 20% or less of the initial value, for example from aninitial Pt—Co color value of 23 to a Pt—Co color value of 5, forexample.

The method is effective with a wide variety of alkanolamines, whichincludes linear, branched or cyclic compounds having at least oneprimary, secondary, or tertiary amino group and at least one alkanolgroup. Such alkanolamines include a mono(C₁₋₁₀ alkanol)amine, a di(C₁₋₁₀alkanol)amine, a tri(C₁₋₁₀ alkanol)amine, an N-(C₁₋₁₀ alkyl) mono(C₂₋₄alkanol)amine, an N-(C₁₋₁₀ alkyl) di(C₂₋₄ alkanol)amine, an N,N-di(C₁₋₁₀alkyl) (C₂₋₄ alkanol)amine, an N-(C₁₋₁₀ alkanol)pyrrolidine, an N-(C₁₋₁₀alkanol)imidazolidine, an N-(C₁₋₁₀ alkanol)piperidine, or an N-(C₁₋₁₀alkanol)piperazine. In some embodiments, the alkanolamine is a mono(C₁₋₄alkanol)amine, a di(C₁₋₄ alkanol)amine, a tri(C₁₋₄ alkanol)amine, anN-(C₁₋₄ alkyl) mono(C₂₋₄ alkanol)amine, an N-(C₁₋₄ alkyl) di(C₂₋₄alkanol)amine, an N,N-di(C₁₋₄ alkyl) (C₂₋₄ alkanol)amine, an N-(C₁₋₄alkanol)pyrrolidine, N-(C₁₋₄ alkanol)imidazolidine, an N-(C₁₋₄alkanol)piperidine, or an N-(C₁₋₄ alkanol)piperazine. Specificalkanolamines are monoethanolamine (MEA), diethanolamine (DEA),triethanolamine (TEA), methyl diethanolamine, isopropanolamine,diisopropanolamine, and (2-hydroxyethyl)piperazine. A combinationcomprising at least one of the foregoing alkanolamines can be used.

In some embodiments, the alkanolamine is triethanolamine. Methods forthe manufacture of triethanolamine are known. For example,triethanolamine compositions can be made by a process that comprisesdistilling triethanolamine from a mixture that includes at leastdiethanolamine and triethanolamine in the presence of phosphorous acid(H₃PO₃). A method of preparation and distillation of triethanolamine isdescribed in, for example, U.S. Pat. No. 6,323,371.

The alkali metal borohydride can be sodium borohydride, potassiumborohydride, or lithium borohydride, but is preferably sodiumborohydride or potassium borohydride. The aqueous solution can have 5 to1000 parts per million by weight of an alkali metal borohydride, or 10to 900 parts per million by weight of an alkali metal borohydride, or 25to 800 parts per million by weight of an alkali metal borohydride, basedon parts by weight of the alkanolamine.

The alkali metal hydroxide can be sodium hydroxide, potassium hydroxide,lithium hydroxide, rubidium hydroxide, or cesium hydroxide, but ispreferably sodium hydroxide or potassium hydroxide. The aqueous solutioncan have 0.5 to 10,000 parts per million by weight of the alkali metalhydroxide, or 1 to 8,000 parts per million by weight of the alkali metalhydroxide, or 10 to 5,000 parts per million by weight of the alkalimetal hydroxide, based on parts by weight of the alkanolamine.

When contacting the alkanolamine with the alkali metal borohydride andalkali metal hydroxide aqueous solution, the alkali metal borohydrideand alkali metal hydroxide aqueous solution is present in an amounteffective to reduce color. The aqueous solution can have a total of 1 to80 weight percent, or 20 to 80 weight percent, or 30 to 70 weightpercent, or 40 to 60 weight percent, of the alkali metal borohydride andthe alkali metal hydroxide, based on the total weight of the aqueoussolution. Other components can be present in the aqueous solution (e.g.,a heat stabilizer, buffer, ultraviolet light absorber, or the like),provided that any such additive does not substantially adversely affectthe color-reducing ability of the aqueous composition.

The alkanolamine compositions can have any level of color beforetreatment with the alkali metal borohydride and alkali metal hydroxideaqueous solution, including low, very low, or no color before treatmentwith the aqueous solution. As described in more detail below, treatmentof alkanolamine compositions having low, very low, or no color can be toprevent color formation over time. For convenience, any alkanolaminecomposition treated with the alkali metal borohydride and alkali metalhydroxide aqueous solution as described herein can be referred to as a“color-reduced alkanolamine composition.”

Contacting the alkanolamine with the alkali metal borohydride and alkalimetal hydroxide aqueous solution can be at a temperature from 20° C. to250° C., or 20° C. to 150° C., or 20° C. to 90° C., or 20° C. to 40° C.Lower temperatures (e.g., 20° C. to 40° C.) are preferred to preventside reactions that can cause color. Contacting can be for a selectedperiod of time, for example, 10 minutes to 50 hours, or 30 minutes to 30hours, or 1 hour to 24 hours. Contacting can be by mixing of thealkanolamine and the alkali metal borohydride and alkali metal hydroxideaqueous solution, during or after the contacting. It is to be understoodthat the alkali metal borohydride and alkali metal hydroxide aqueoussolution is generally not subsequently quenched or removed from thealkanolamine, such that the above contacting temperatures and times maysimply be for an initial period before the alkanolamine is furtherprocessed, for example transported or packaged for storage ortransportation.

Contacting the alkanolamine with the alkali metal borohydride and alkalimetal hydroxide aqueous solution reduces initial color, e.g., colorbodies and color contaminants, present in the alkanolamine before suchcontact, and provides the color-reduced alkanolamine compositionsherein. The inventors hereof have advantageously found that such initialcolor is reduced during or after contacting to the extent that theresultant alkanolamine compositions are colorless or near colorless.Without wishing to be bound by any specific theory, borane is believedto be liberated during contacting and acts as a reducing agent, of anycolor bodies or contaminants that cause color bodies to be present inthe alkanolamine.

The color-reduced alkanolamine compositions produced by the methodsdescribed herein, for example color-reduced triethanolaminecompositions, can have significantly reduced or low color. For example,the Hazen color, specifically the Platinum-Cobalt Color Value asdetermined according to Test Method ASTM D1209 (“Pt—Co color value”) canbe less than 50, or less than 30. It has surprisingly been found thatthe Pt—Co color value can be 0 to 20.

Further advantageously, the color-reduced alkanolamine compositionsproduced by these methods, specifically color-reduced triethanolaminecompositions, can maintain these very low color values over extendedperiods. The alkali metal borohydride and alkali metal hydroxide aqueoussolution can thus prevent color increases over time. For example, thecolor-reduced alkanolamine compositions produced by the methodsdescribed herein, specifically color-reduced triethanolaminecompositions, when stored at room temperature (e.g., 20° C. to 25° C.)for a period of three months to eight years, or one year to eight years,or three months to six months, or six months to one year, or one year tothree years, or one year to six years, following the contacting, canhave a Pt—Co color value of less than 50, or less than 30, or 0 to 20.

In some embodiments, the color-reduced alkanolamine compositions canhave a Pt—Co color value of less than 50, or less than 30, or 0 to 20,after storage at room temperature (e.g., 20° C. to 25° C.) for a periodof three months to eight years, or one year to eight years, or threemonths to six months, or six months to one year, or one year to threeyears, or one year to six years, following the contacting when protectedfrom light. “Storage” as used herein includes periods where thecompositions are not in active use, for example where the compositionsare transported. “Protected from light” can mean that the compositionsare stored under conditions where visible light is excluded for at least90% of the time during storage.

In other embodiments, the color-reduced alkanolamine compositionsproduced by the methods described herein, specifically color-reducedtriethanolamine compositions, can have a Pt—Co color value that does notincrease by more than 4 times, or more than 3 times, or more than 2times, when stored at room temperature (e.g., 20° C. to 25° C.) for aperiod of three months to eight years, or one year to eight years, orthree months to six months, or six months to one year, or one year tothree years, or one year to six years, following the contacting. In someembodiments, the color-reduced alkanolamine compositions produced by themethods described herein, specifically color-reduced triethanolaminecompositions, can have a Pt—Co color value that does not increase bymore than 4 times, or more than 3 times, or more than 2 times, whenstored at room temperature (e.g., 20° C. to 25° C.) for a period ofthree months to eight years, or one year to eight years, or three monthsto six months, or six months to one year, or one year to three years, orone year to six years when protected from light.

The alkanolamine compositions produced by these methods are alsocolor-stable at elevated temperatures. Thus, the color-reducedalkanolamine compositions produced by the methods described herein,specifically color-reduced triethanolamine compositions, when stored at30° C. to 60° C., or 40° C. to 50° C., or 45° C., for a period of onemonth to six years, or one month to two years, or three months to oneyear, or six months following the contacting, can have a Pt—Co colorvalue of less than 50, or less than 30, or 0 to 20, or compositions canhave a Pt—Co color value of less than 50, or less than 30, or 0 to 20,after storage at 30° C. to 60° C., or 40° C. to 50° C., or 45° C., for aperiod of one month to six years, or one month to two years, or threemonths to one year, or six months following the contacting whenprotected from light. In other embodiments, the color-reducedalkanolamine compositions produced by the methods described herein,specifically color-reduced triethanolamine compositions, can have aPt—Co color value that does not increase by more than 4 times, or morethan 3 times, or more than 2 times, when stored at 30° C. to 60° C., or40° C. to 50° C., or 45° C. for a period of one month to six years, orone month to two years, or three months to one year, or six monthsfollowing the contacting. In some embodiments, the color-reducedalkanolamine compositions produced by the methods described herein,specifically color-reduced triethanolamine compositions, can have aPt—Co color value that does not increase by more than 4 times, or morethan 3 times, or more than 2 times, when stored at 30° C. to 60° C., or40° C. to 50° C., or 45° C., for a period of one month to six years, orone month to two years, or three months to one year, or six months yearswhen protected from light.

The color-reduced compositions can comprise an alkanolamine and residualmaterials such as unreacted alkali metal borohydride, or unreactedalkali metal hydroxide, or reaction products thereof, or degradationproducts. The residual materials in the color-reduced compositions canaccordingly be 0.1 to 5,000 ppm, or 5 to 2,000 ppm, or 5 to 1,000 ppm.

Accordingly, color-reduced alkanolamine compositions comprising analkanolamine and 0.1 to 5000 ppm of residual materials, or 5 to 2,000ppm of residual materials, or 5 to 1,000 ppm of residual materials, canhave a Pt—Co color value of less than 50, or less than 30. In anembodiment, the Pt—Co color value can be 0 to 20. In some embodiments,color-reduced triethanolamine compositions comprising triethanolamineand 0.1 to 5,000 ppm of residual materials, or 5 to 2,000 ppm ofresidual materials, or 5 to 1,000 ppm of residual materials, can have aPt—Co color value of less than 50, or less than 30. In an embodiment,the Pt—Co color value of the color-reduced triethanolamine compositioncomprising residual materials can be 0 to 20.

The color-reduced alkanolamine compositions can maintain these very lowcolor values over extended time. For example, the color-reducedalkanolamine compositions produced by these methods, specificallycolor-reduced triethanolamine compositions, comprising an alkanolamineand 0.1 to 5000 ppm of residual materials, or 5 to 2,000 ppm of residualmaterials, or 5 to 1,000 ppm of residual materials, after storage atroom temperature (e.g., 20° C. to 25° C.) for a period of three monthsto eight years, or one year to eight years, or three months to sixmonths, or six months to one year, or one year to three years, or oneyear to six years following the contacting, can have a Pt—Co color valueof less than 50, or less than 30, or 0 to 20. The color-reducedalkanolamine compositions produced by these methods, specificallycolor-reduced triethanolamine compositions, comprising an alkanolamineand 0.1 to 5000 ppm of residual materials, or 5 to 2,000 ppm of residualmaterials, or 5 to 1,000 ppm of residual materials can have a Pt—Cocolor value of less than 50, or less than 30, or 0 to 20 after storageat room temperature (e.g., 20° C. to 25° C.) for a period of threemonths to eight years, or one year to eight years, or three months tosix months, or six months to one year, or one year to three years, orone year to six years when the compositions are protected from light.

The color-reduced alkanolamine compositions produced by these methods,specifically color-reduced triethanolamine compositions, comprising analkanolamine and 0.1 to 5000 ppm of residual materials, or 5 to 2,000ppm of residual materials, or 5 to 1,000 ppm of residual materials, canhave a Pt—Co color value that does not increase by more than 4 times, ormore than 3 times, or more than 2 times, after storage at roomtemperature (e.g., 20° C. to 25° C.) for a period of three months toeight years, or one year to eight years, or three months to six months,or six months to one year, or one year to three years, or one year tosix years following the contacting. The color-reduced alkanolaminecompositions produced by these methods, specifically color-reducedtriethanolamine compositions, comprising an alkanolamine and 0.1 to 5000ppm of residual materials, or 5 to 2,000 ppm of residual materials, or 5to 1,000 ppm of residual materials can have a Pt—Co color value thatdoes not increase by more than 4 times, or more than 3 times, or morethan 2 times, after storage at room temperature (e.g., 20° C. to 25° C.)for a period of three months to eight years, or one year to eight years,or three months to six months, or six months to one year, or one year tothree years, or one year to six years when the compositions areprotected from light.

In some embodiments, color-reduced triethanolamine compositions producedby these methods, specifically color-reduced triethanolaminecompositions, comprising an alkanolamine and 0.1 to 5000 ppm of residualmaterials, or 5 to 2,000 ppm of residual materials, or 5 to 1,000 ppm ofresidual materials, after storage at 30° C. to 60° C., or 40° C. to 50°C., or 45° C. for a period of one month to six years, or one month totwo years, or three months to one year, or six months following thecontacting, can have a Pt—Co color value less than 50, or less than 30,or 0 to 20. The color-reduced alkanolamine compositions produced bythese methods, specifically color-reduced triethanolamine compositions,comprising an alkanolamine and 0.1 to 5000 ppm of residual materials, or5 to 2,000 ppm of residual materials, or 5 to 1,000 ppm of residualmaterials, triethanolamine compositions can have Pt—Co color value ofless than 50, or less than 30, or 0 to 20 after storage at 30° C. to 60°C., or 40° C. to 50° C., or 45° C. for a period of one month to sixyears, or one month to two years, or three months to one year, or sixmonths when the compositions are protected from light.

In other embodiments, the color-reduced alkanolamine compositionsproduced by the methods described herein, specifically color-reducedtriethanolamine compositions comprising an alkanolamine, specificallytriethanolamine and 0.1 to 4,500 ppm of residual materials, or 5 to2,000 ppm of residual materials, or 5 to 1,000 ppm of residualmaterials, can have a Pt—Co color value that does not increase by morethan 4 times, or more than 3 times, or more than 2 times, when stored at30° C. to 60° C., or 40° C. to 50° C., or 45° C. for a period of onemonth to six years, or one month to two years, or three months to oneyear, or six months following the contacting. In some embodiments, thecolor-reduced alkanolamine compositions produced by the methodsdescribed herein, specifically color-reduced triethanolaminecompositions, comprising an alkanolamine, specifically triethanolamineand 0.1 to 4,500 ppm of residual materials, or 5 to 2,000 ppm ofresidual materials, or 5 to 1,000 ppm of residual materials, can have aPt—Co color value that does not increase by more than 4 times, or morethan 3 times, or more than 2 times, when stored at 30° C. to 60° C., or40° C. to 50° C., or 45° C., for a period of one month to six years, orone month to two years, or three months to one year, or six months yearswhen protected from light.

The color-reduced alkanolamine compositions can include water. Forexample, water can be present in the compositions in an amount of lessthan 10 weight percent (wt. %), or less than 5 wt. %, or less than 3 wt.%, or less than 1 wt. %, or less than 0.5 wt. %, based on the totalweight of the color-reduced alkanolamine composition.

As mentioned above, an advantage of this method is that the alkanolaminecompositions do not require subsequent purification or processing, e.g.,distillation, after being contacted with the alkali metal borohydrideand alkali metal hydroxide aqueous solution. In particular, thecolor-reduced alkanolamine does not require subsequent distillation orpurification to remove residual materials such as unreacted borohydridesor hydroxides, or reaction products, or degradation products. Thus, insome embodiments an as-synthesized alkanolamine can be contacted toreduce color, then not distilled or otherwise purified, and still attainlow color or retain the low color after storage as described above. Thiscan save significant time and cost in the manufacture of thealkanolamines For example, in these embodiments, the as-synthesizedalkanolamine can be contacted and packaged for storage or transportwithin 3 hours, within 6 hours, or within 24 hours of contacting, andwithout distillation. In other embodiments the as-synthesizedalkanolamine is stored after synthesis before contacting, for examplefor at least 24 hours, at least 1 week, or at least one month. Thestored compositions can then still be contacted as described above toreduce any color and provide low color on further storage.

The alkanolamine compositions can be used for virtually any purpose, forexample as emulsifiers, surfactants, solvents, co-solvents, pH adjustingagents, or buffering agents, as well as in any other known uses, in awide variety of applications. Such applications include household goods,cement production, cosmetics, medicine, printing, chemical manufacturing(e.g., as a solvent, catalyst, or reactant, and electroless plating.Some products that can include the alkanolamines include liquid laundrydetergents, dishwashing liquids, general cleaners, hand cleaners,polishes, metalworking fluids, paints, shaving cream, and printing inks.

The following Examples are provided for illustrative purposes only andare not to be construed as limiting in any manner.

EXAMPLES

Color determination was carried out on a LICO 690 Colorimeter fromKoehler Instrument Company in accordance with the Pt—Co test method asdescribed in ASTM D1209 (2011). Results are reported as Pt—Co ColorValues.

Example. Color Stability of a Color-Reduced Triethanolamine Composition

An aqueous solution of sodium borohydride (12%, weight percentage) andsodium hydroxide (40%, weight percentage) was prepared.

Triethanolamine (1000 g, Sigma Aldrich, 99% purity) having a Pt—Co ColorValue (ASTM D1209) of 23 was mixed with the above prepared aqueoussolution (1.6724 g, containing 200.7 mg sodium borohydride and 669.0 mgsodium hydroxide, equal to 200 ppm of sodium borohydride and 669 ppm ofsodium hydroxide to triethanolamine) The mixture was vigorously shakento allow the aqueous solution to be distributed homogenously in thetriethanolamine Over a period of 6 hours the mixture cleared.

A sample was taken for color analysis after the mixture was cleared. Itwas found the color index was about 5 and found to have a Pt—Co Colorvalue (ASTM D1209) less than 15 for 2 years at room temperature (20-25°C.).

Comparative experiments of using sodium borohydride or sodium hydroxideseparately to improve the color quality of triethanolamine wereperformed. Neither of the single components sodium borohydride or sodiumhydroxide could reduce the color of triethanolamine as effectively andcontinuously as the combination of sodium borohydride and sodiumhydroxide.

The methods and compositions are further illustrated by the followingembodiments.

Embodiment 1: A method of reducing color in an alkanolamine, the methodcomprising: contacting the alkanolamine with an amount of an aqueoussolution effective to provide 5 to 1000 parts per million by weight ofan alkali metal borohydride, based on parts by weight of thealkanolamine; and 0.5 to 10,000 parts per million by weight of an alkalimetal hydroxide, based on parts by weight of the alkanolamine;preferably wherein the color-reduced alkanolamine is not distilled afterthe contacting.

Embodiment 2: The method of Embodiment 1, wherein the color-reducedalkanolamine is packaged for storage or transportation withoutdistillation.

Embodiment 3: The method of Embodiment 1 or Embodiment 2, wherein thecolor-reduced alkanolamine has a Platinum-Cobalt Color Value, TestMethod ASTM D1209, of less than 50, preferably less than 30, morepreferably 0 to less than or equal to 20.

Embodiment 4: The method of any one or more of Embodiments 1 to 3,wherein the alkanolamine is a mono(C₁₋₁₀ alkanol)amine, a di(C₁₋₁₀alkanol)amine, a tri(C₁₋₁₀ alkanol)amine, an N-(C₁₋₁₀ alkyl) mono(C₂₋₄alkanol)amine, an N-(C₁₋₁₀ alkyl) di(C₂₋₄ alkanol)amine, an N,N-di(C₁₋₁₀alkyl) (C₂₋₄ alkanol)amine, an N-(C₁₋₁₀ alkanol)pyrrolidine, an N-(C₁₋₁₀alkanol)imidazolidine, an N-(C₁₋₁₀ alkanol)piperidine, an N-(C₁₋₁₀alkanol)piperazine, or a combination comprising at least one of theforegoing; preferably monoethanolamine, diethanolamine, triethanolamine,methyldiethanolamine, isopropanolamine, diisopropanolamine,(2-hydroxyethyl)piperazine, or a combination comprising at least one ofthe foregoing.

Embodiment 5: The method of any one or more of Embodiments 1 to 4,wherein the alkanolamine is a tri(C₁₋₁₀ alkanol)amine, preferablytriethanolamine.

Embodiment 6: The method of any one or more of Embodiments 1 to 5,wherein the aqueous solution comprises a total of 20 to 80 weightpercent, or 30 to 70 weight percent, or 40 to 60 weight percent, of thealkali metal borohydride and the alkali metal hydroxide, based on thetotal weight of the aqueous solution.

Embodiment 7: The method of any one or more of Embodiments 1 to 6,wherein the alkali metal borohydride is sodium borohydride or potassiumborohydride, and the alkali metal hydroxide is sodium hydroxide orpotassium hydroxide.

Embodiment 8: The method of any one or more of Embodiments 1 to 7,wherein contacting is with 10 to 900, or 25 to 800 parts per million byweight of the alkali metal borohydride, based on parts by weight of thealkanolamine; and 1 to 8,000, or 10 to 5,000 parts per million by weightof the alkali metal hydroxide, based on parts by weight of thealkanolamine.

Embodiment 9: The method of any one or more of Embodiments 1 to 8,comprising less than 5 wt % of water, preferably less than 1 wt % ofwater, based on the total weight of the triethanolamine.

Embodiment 10: The method of any one or more of Embodiments 1 to 9,further comprising storing the color-reduced composition.

Embodiment 11: A color-reduced alkanolamine composition, thecomposition, comprising in combination: an alkanolamine, and an aqueoussolution in an amount effective to provide 5 to 1000 parts per millionby weight of an alkali metal borohydride, based on parts by weight ofthe alkanolamine; and 0.5 to 10,000 parts per million by weight of analkali metal hydroxide, based on parts by weight of the alkanolamine.

Embodiment 12: The composition of Embodiment 11, wherein the compositionhas a Platinum-Cobalt Color Value, Test Method ASTM D1209, of less than50, preferably less than 30, more preferably 0 to less than or equal to20.

Embodiment 13: The composition of Embodiment 11 or 12, wherein thePlatinum-Cobalt Color Value, Test Method ASTM D1209, does not increaseby more than more than 4 times, or more than 3 times, or more than 2times, for a period of six months to one year, or one to two years, orone to three years after storage at room temperature.

Embodiment 14: The composition of Embodiment 11 or 12, wherein thePlatinum-Cobalt Color Value, Test Method ASTM D1209, does not increaseby more than 4 times for a period of three to six months, or six monthsto one year, or one to two years, or one to three years after storage at30° C. to 60° C., or 40° C. to 50° C.

Embodiment 15: The composition of any one or more of Embodiments 11 to14, wherein the alkanolamine is a mono(C₁₋₁₀ alkanol)amine, a di(C₁₋₁₀alkanol)amine, a tri(C₁₋₁₀ alkanol)amine, an N-(C₁₋₁₀ alkyl) mono(C₂₋₄alkanol)amine, an N-(C₁₋₁₀ alkyl) di(C₂₋₄ alkanol)amine, an N,N-di(C₁₋₁₀alkyl) (C₂₋₄ alkanol)amine, an N-(C₁₋₁₀ alkanol)pyrrolidine, an N-(C₁₋₁₀alkanol)imidazolidine, an N-(C₁₋₁₀ alkanol)piperidine, an N-(C₁₋₁₀alkanol)piperazine, or a combination comprising at least one of theforegoing; preferably monoethanolamine, diethanolamine, triethanolamine,methyldiethanolamine, isopropanolamine, diisopropanolamine,(2-hydroxyethyl)piperazine, or a combination comprising at least one ofthe foregoing.

Embodiment 16: The composition of any one or more of Embodiments 11 to15, wherein the alkanolamine is a tri(C₁₋₁₀ alkanol)amine, preferablytriethanolamine.

Embodiment 17: The composition of any one or more of Embodiments 11 to16, wherein the aqueous solution comprises a total of 20 to 80 weightpercent, or 30 to 70 weight percent, or 40 to 60 weight percent, of thealkali metal borohydride and the alkali metal hydroxide, based on thetotal weight of the solution.

Embodiment 18: The composition of any one or more of Embodiments 11 to17, wherein the alkali metal borohydride is sodium borohydride orpotassium borohydride, and the alkali metal hydroxide is sodiumhydroxide or potassium hydroxide.

Embodiment 19: The composition of any one or more of Embodiments 11 to18, wherein contacting is with 10 to 900, or 25 to 800 parts per millionby weight of the alkali metal borohydride, based on parts by weight ofthe alkanolamine; and 1 to 8,000, or 10 to 5,000 parts per million byweight of the alkali metal hydroxide, based on parts by weight of thealkanolamine.

Embodiment 20: The composition of any one or more of Embodiments 11 to19, comprising less than 5 wt % of water, preferably less than 1 wt % ofwater, based on the total weight of the triethanolamine.

In general, the methods and compositions can alternatively comprise,consist of, or consist essentially of, any appropriate steps orcomponents herein disclosed. The methods or compositions canadditionally, or alternatively, be formulated so as to be devoid, orsubstantially free, of any steps, components, materials, ingredients,adjuvants or species used in the prior art compositions or that areotherwise not necessary to the achievement of the function and/orobjectives described herein.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. “Or” means “and/or.” Theendpoints of all ranges directed to the same component or property areinclusive and independently combinable. Disclosure of a narrower rangeor more specific group in addition to a broader range is not adisclaimer of the broader range or larger group. Unless definedotherwise, technical and scientific terms used herein have the samemeaning as is commonly understood by one of skill in the art to whichthis invention belongs. A “combination” is inclusive of blends,mixtures, alloys, reaction products, and the like.

All cited patents, patent applications, and other references areincorporated herein by reference in their entirety. However, if a termin the present application contradicts or conflicts with a term in theincorporated reference, the term from the present application takesprecedence over the conflicting term from the incorporated reference.

As used herein, the term “hydrocarbyl” includes groups containingcarbon, hydrogen, and optionally one or more heteroatoms (e.g., 1, 2, 3,or 4 atoms such as halogen, O, N, S, P, or Si). “Alkyl” means a branchedor straight chain, saturated, monovalent hydrocarbon group, e.g.,methyl, ethyl, i-propyl, and n-butyl. “Alkylene” means a straight orbranched chain, saturated, divalent hydrocarbon group (e.g., methylene(—CH₂—) or propylene (—(CH₂)₃—)). “Alkenyl” and “alkenylene” mean amonovalent or divalent, respectively, straight or branched chainhydrocarbon group having at least one carbon-carbon double bond (e.g.,ethenyl (—HC═CH₂) or propenylene (—HC(CH₃)═CH₂—). “Alkynyl” means astraight or branched chain, monovalent hydrocarbon group having at leastone carbon-carbon triple bond (e.g., ethynyl). “Alkoxy” means an alkylgroup linked via an oxygen (i.e., alkyl-O-), for example methoxy,ethoxy, and sec-butyloxy. “Cycloalkyl” and “cycloalkylene” mean amonovalent and divalent cyclic hydrocarbon group, respectively, of theformula —C_(n)H_(2n-x) and —C_(n)H_(2n-x)— wherein x is the number ofcyclization(s) and n is an integer representing normal valence, forexample from 3 to 8. “Aryl” means a monovalent, monocyclic orpolycyclic, aromatic group (e.g., phenyl or naphthyl). “Arylene” means adivalent, monocyclic or polycyclic, aromatic group (e.g., phenylene ornaphthylene). The prefix “halo” means a group or compound including onemore halogen (F, Cl, Br, or I) substituents, which can be the same ordifferent. The prefix “hetero” means a group or compound that includesat least one ring member that is a heteroatom (e.g., 1, 2, or 3)heteroatoms, wherein each heteroatom is independently the same ordifferent and is N, O, S, or P.

“Substituted” means that the compound or group is substituted with atleast one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, whereeach substituent is independently the same or different and is nitro(—NO2), cyano (—CN), hydroxy (—OH), halogen, thiol (—SH), thiocyano(—SCN), C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₁₋₆ haloalkyl, C₁₋₉alkoxy, C₁₋₆ haloalkoxy, C₃₋₁₂ cycloalkyl, C₅₋₁₈ cycloalkenyl, C₆₋₁₂aryl, C₇₋₁₃ arylalkylene (e.g., benzyl), C₇₋₁₂ alkylarylene (e.g.,toluyl), C₄ heterocycloalkyl, C₃₋₁₂ heteroaryl, C₁₋₆ alkyl sulfonyl(—S(═O)₂-alkyl), C₆₋₁₂ arylsulfonyl (—S(═O)₂-aryl), or tosyl(CH₃C₆H₄SO₂—), provided that the substituted atom's normal valence isnot exceeded, and that the substitution does not significantly adverselyaffect the manufacture, stability, or desired property of the compound.When a compound is substituted, the indicated number of carbon atoms isthe total number of carbon atoms in the group, including those of thesubstituent(s).

While the invention has been described with reference to an exemplaryembodiment or embodiments, it will be understood by those skilled in theart that various changes can be made and equivalents can be substitutedfor elements thereof without departing from the scope of the invention.In addition, many modifications can be made to adapt a particularsituation or material to the teachings of the invention withoutdeparting from the essential scope thereof.

1. A method of reducing color in an alkanolamine, the method comprising:contacting the alkanolamine with an amount of an aqueous solutioneffective to provide 5 to 1000 parts per million by weight of an alkalimetal borohydride, based on parts by weight of the alkanolamine; and 0.5 to 10,000 parts per million by weight of an alkali metal hydroxide,based on parts by weight of the alkanolamine.
 2. The method of claim 1,wherein the color-reduced alkanolamine is packaged for storage ortransportation without distillation.
 3. The method of claim 1, whereinthe color-reduced alkanolamine has a Platinum-Cobalt Color Value, TestMethod ASTM D1209, of less than
 50. 4. The method claim 1, wherein thealkanolamine is a mono(C₁₋₁₀ alkanol)amine, a di(C₁₋₁₀ alkanol)amine, atri(C₁₋₁₀ alkanol)amine, an N-(C₁₋₁₀ alkyl) mono(C₂₋₄ alkanol)amine, anN-(C₁₋₁₀ alkyl) di(C₂₋₄ alkanol)amine, an N,N-di(C₁₋₁₀ alkyl) (C₂₋₄alkanol)amine, an N-(C₁₋₁₀ alkanol)pyrrolidine, an N-(C₁₋₁₀alkanol)imidazolidine, an N-(C₁₋₁₀ alkanol)piperidine, an N-(C₁₋₁₀alkanol)piperazine, or a combination comprising at least one of theforegoing.
 5. The method of claim 1, wherein the alkanolamine is atri(C₁₋₁₀ alkanol)amine.
 6. The method of claim 1, wherein the aqueoussolution comprises a total of 1 80 weight percent of the alkali metalborohydride and the alkali metal hydroxide, based on the total weight ofthe aqueous solution.
 7. The method of claim 1, wherein the alkali metalborohydride is sodium borohydride or potassium borohydride, and thealkali metal hydroxide is sodium hydroxide or potassium hydroxide. 8.The method of claim 1, wherein contacting is with 10 to 900, or 25 to800 parts per million by weight of the alkali metal borohydride, basedon parts by weight of the alkanolamine; and 1 to 8,000, or 10 to 5,000parts per million by weight of the alkali metal hydroxide, based onparts by weight of the alkanolamine.
 9. The method of claim 1,comprising less than 5 wt % of water based on the total weight of thetriethanolamine.
 10. The method of claim 1, further comprising storingthe color-reduced composition. 11-20. (canceled)
 21. The method of claim1, wherein the alkanolamine is monoethanolamine, diethanolamine,triethanolamine, methyldiethanolamine, isopropanolamine,diisopropanolamine, (2-hydroxyethyl)piperazine, or a combinationcomprising at least one of the foregoing.
 22. The method of claim 1,wherein the color-reduced alkanolamine is not distilled after thecontacting.
 23. The method of claim 1, wherein the alkanolamine istriethanolamine.
 24. The method of claim 1, wherein the color-reducedalkanolamine has a Platinum-Cobalt Color Value, Test Method ASTM D1209,of less than
 30. 25. The method of claim 1, wherein the alkali metalborohydride is potassium borohydride, and the alkali metal hydroxide ispotassium hydroxide.
 26. The method of claim 6, wherein the alkanolamineis triethanolamine.
 27. The method of claim 7, wherein the alkanolamineis triethanolamine.
 28. The method of claim 8, wherein the alkanolamineis triethanolamine.
 29. The method of claim 9, wherein the alkanolamineis triethanolamine.
 30. The method of claim 10, wherein the alkanolamineis triethanolamine.